Process for the preparation of esters from myrcene hydrohalides



United States Patent 3,475,484 PROCESS FOR THE PREPARATION OF ESTERS FROM MYRCENE HYDROHALIDES Garry C. Kitchens, Wayne, and Robert T. Dahill, Jr.,

Perth Amboy, N.J., assignors to Givaudan Corporation, Clifton, N.J., a corporation of New Jersey No Drawing. Filed Nov. 17, 1967, Ser. No. 683,785 Int. C07c 69/ 02; B01j 11/82; C01g N06 US. Cl. 260-489 9 Claims ABSTRACT OF THE DISCLOSURE The use of a novel catalyst, a phosphorous trichlorideammonia addition product, in the double decomposition reaction of myrcene hydrohalides, singly or in combination, and carboxylic acid salts, is disclosed. The catalyst, -PCI (NH may be formed in situ.

The resulting esters are obtained in good yield and have a high ratio of the more desirable linalyl esters as compared with the neryl esters and geranyl esters.

BACKGROUND OF THE INVENTION The reactions of myrcene hydrochloride with alkali salts of fatty acids with solvents, as acetic acid and acetic anhydride, and without solvents, to give 40-80% weight yields (based on mycrene) of esters have been reported in literature:

Fornet, Seifensider Zeitung, 63, 707-9, 739-41 (1936) Knapp et al., US. 2,609,388 (1950) Bell et al., US. 2,871,271 (1952) Bay, US. 2,062,874 (1962) Boake Roberts 00., Brit. 896,262 (1962) These methods all have disadvantages. The reactions of the chlorides with sodium acetate without solvents give poor weight yields of the esters, of the order of 40 to 50% based on myrcene. The use of large quantities of the expensive solvents, acetic acid and acetic anhydride, increases the weight yields to 50-60%, based on the myrcene. The use of ammonium acetate increases the weight yield to'70-80%, based on the myrcene used.

The use of triethylamine acetate to convert simple alkyl chlorides to acetates has beeen revealed. (Mills et al., Chem. & Ind., 52, 2144 (1962). This method is not economically feasible, since large quantities of the expensive triethylamine is required and the amine would have to be recovered. In applying the process to the production of linalyl, neryl and geranyl esters, it was found that 20-40% of the amine added in the form of its acetate is lost and cannot be recovered.

The preparation of linalyl, neryl and geranyl esters, containing a large amount of the ct form of these esters, is described by rBain, US. 3,062,875 (1962). Myrcene is treated with 2 moles of hydrogen chloride to form myrcene dihydrochloride which is converted to estersby treatment with metal salts of carboxylic acids in the presence of 1% or more of an amine. This method has the disadvantage that 2 moles of hydrogen chloride, is required to form the myrcene dihydrochloride and the dihydrochloride requires two moles of the metal salt to be converted to the esters. The method has the further disadvantage in that the products are 70-75% of the a-forms of the esters, while the linalyl, neryl and geranyl esters known and used in perfumery are mainly the fl-forms. This process also has the disadvantage in that dehydrohalogenation must occur in order to obtain the mono acyloxy ester.

A method for the preparation of predominantly linalyl ester is disclosed by Webb, US. 3,076,839 (1966). Myrcene hydrochlorides are treated with a carboxylic 3,475,484 Patented Oct. 28, 1969 acid salt in the presence of a cuprous halide and a carboxylic acid solvent. The disadvantages of this method are the use of 4 to 5% of expensive cuprous halides and the large quantities of expensive carboxylic acid solvent. The recovery of the acid solvent and the isolation of the products also add to the cost.

A method for the preparation of predominantly neryl and geranyl ester is disclosed by Webb, US. 3,031,442, where myrcene hydrochloride is treated with a canboxylic acid salt under nonaqueous conditions in the presence of a nitrogen base catalyst. The main disadvantage of this method is that it gives only small amounts of the more expensive linalyl esters.

The teachings of Webb, US. 3,076,839 1963) and US. 3,031,442 (1962), are that in the conversion of myrcene hydrochloride to esters cuprous chloride is a catalyst for linalyl ester production and the nitrogen base is a catalyst for the neryl and geranyl ester production. Thus while in acetic acid solution, cuprous chloride causes dominately (sic) linalyl ester production, even if a little nitrogen base is present and while in a definitely basic system, such as is present when myrcene hydrochloride is treated with sodium acetate and an amine, the nitrogen base causes preponderately geranyl ester formation even if a little cuprous chloride is present, there are reaction conditions whereby both types of catalysts takes place so that the ester produced is rich inboth linalyl and geranyl esters. The inventor attempts to explain these intermediate reaction conditions as between definite basicity and definite acidity conditions.

Yamashita and Shimamura, Kogyo Kagahu, Zasshi, 60, 423-6 (1957), C.A., 53, 9025 (1959) describe the catalytic efiect of tertiary amines on sodium chloride eliminating esterification. The promoting etfects of pyridine in various amounts on the esterification reactions between benzyl chloride and sodium acetate or sodium benzoate were examined with or without xylene, xylenewater, Xylene-acetic acid, xylene-benzyl alcohol, xyleneethyl alcohol or water at different temperatures. Similar experiments were also carried out for the reactions of C H Cl CH C H Cl, ClC H NO ClC H (NO or cetyl chloride and sodium acetate in the presence of pyridine. The catalytic effects on benzyl chloride and sodium acetate reaction and other amines, dibutyl sulfide, triethylarsine and triethyl phosphine were studied.

A method of treating myrcene hydrogenhalides (linalyl, neryl and geranyl halides) with a carboxylic acid salt in the presence of dimethyl sulfoxide (solvent catalyst) to yield linalyl, neryl and geranyl esters is described by Webb, US. 3,280,177 1966). This method has the disadvantage that it would be necessary to recover the dimethyl sulfoxide solvent which would add to the cost of the esters.

Webb, US. 3,293,286 (1966) describes a method of preparing predominantly neryl and geranyl esters by treating linalyl, neryl and geranyl halides with a carboxylic acid salt and a phosphorus containing catalyst selected from the group consisting of phosphorus, phosphonium salts and trivalent phosphorus compounds having the formula where R, R, and R are selected from the group consisting of hydrogen, alkyl, cycle-alkyl, aryl, alkylamino, arylamino, cyclo-alkylamino and amino. This process has the disadvantage that the catalyst is expensive and hazardous, requiring special safety precautions, also it produces predominantly neryl and geranyl esters and only small quantities of the more expensive linalyl esters.

3 SUMMARY OF THE INVENTION This invention relates to the novel use of the phosphorus trichloride-ammonia addition compound, as a promoter in the reaction of myrcene hydrohalides and alkali salts of fatty acids, to produce the valuable perfume materials, linalyl, neryl, and geranyl esters. The use of this novel compound provides a novel method for obtaining a product high in linalyl ester content.

4 mane, Green and Co., New York, 1947, pp. 220, 271, 708, 1004, 1014; H. Peperot, compt. rend., 181x, 662 (1925). The reactions involved can be illustrated, using linalyl, neryl and geranyl chlorides, sodium acetate and the catalyst to yield esters, as follows:

s-( 3); [(PClz-(NH3)5)OOCCH NaCl I DESCRIPTION OF THE PREFERRED EMBODIMENTS 1 2 I In one aspect of the present invention, it involves a process for preparing esters by reacting at least one memw ber of the group consisting of myrcene hydrohalide, linalyl halide, neryl halide and geranyl halide, with a car- 15 Lina1y1 om id Neryl, Geranyl Chloridcs boxylic acid salt, in the presence of an addition compound of phosphorus trichloride and ammonia as a catalyst. l[(PCl2-( Z)B) 3] In another aspect, the present invention provides a novel compound, PCl -(NH I The novel catalyst, phosphorus trichloride-ammonia adidtion compound, formula PCl -5NH prepared by 000011, 3 the addition of 5 moles of ammonia to 1 mole of phosphorus trichloride, is inexpensive, easy to prepare, stable solid which can be stored and handled without special precautions. The catalyst can also be prepared in situ in the process. Linalyl Acetate Neryl, Geranyl Acotates The iHVeHtiOI} PP to myrcene hydrohafides, Thus, in excess sodium acetate the products of the hydrogen h10flde, hydrogen bfomlde and hydrogen reaction are esters, sodium chloride, unreacted sodium iodide. The invention is illustrated by means of the acetate and h phosphorus containing l g hydrogen chloride derivative of myrcene, since this is the In order to l if f th the nature f the present more important hydrohalide from a commercial point of invention th following examples are given, by way view. of illustration and not by way of limitation. Unless other- The Preparation of myrcene hyflfochlollde 15 Well wise specified, all temperatures are in degrees Centigrade, kn (G Essentlal 0115, II, Van all boiling points are uncorrected, and all amounts are Nostrand Co., New York, 1949, pp. 778-79; Fomet, i parts by weight Seifensider Zeitung, 63, 707-9 (1936), 63, 739-41 (1936); Knapp et al., U.S. 2,609,388 1950 Booth, EXAMPLE I U.S. 2,871,271 (1953);Boake Roberts Co., Brit. 896,262 Into a one liter flask equipped with an agitator, (1962); Weiss, U.S. 2,882,323; Webb, U.S. 3,016,408). thermometer, gas inlet tube and sealed to the air by a Myrcene hydrochloride is prepared by the treatment of bubbling tube containing 1 inch of heavy mineral oil, myrcene with one equivalent of anhydrous hydrogen was charged 250 g. myrcene, distilled (80%) and 2.5 g. chloride in the presence of a cuprous or a cupric salt. of cupric acetate. The flask was evacuated and 56 g. an- The chloride, known as myrcene hydrochloride, consists hydrous hydrogen chloride was passed in Over the surof a mixture of linalyl, neryl and geranyl chlorides with 45 face at 10 C. over a 4 hour period with cooling and lesser amounts of myrcenyl chloride, dipentene hydrovigorous agitation. The batch was agitated an additional chloride, bornyl chloride and myrcene dihydrochloride. hour at 10 C. The crude chlorides amounted to In accordance with the process of this invention, 308.5 g. myrcene hydrochloride is reacted with 1 to 1.5 moles of To the myrcene hydrochloride was added 159.1 g. of an alkali salt of a fatty acid and 0.001 to 0.1 mole of anhydrous sodium acetate and the batch heated to 90 C. the phosphorus trichloride-ammonia addition compound The batch was agitated at 90-95 C. for 8 hours. until at least 80% of the chlorides have reacted. A reac- Samples were taken at intervals during the agitation tion temperature of 70 to 100 C. is preferred. Lower period, washed, dried and analyzed by vapor pressure temperatures require longer reaction periods, while highchromatography (V.P.C.).

Total Percent Percent Marat tar: Ziiiiii Liliililiiiii (Hrs) chlorides Aeeta e and 15331;? afit a i i aci t iii s 5 33:3 '3 "3 3 1% 5:3 4 a? s s 8 96:9 0 0 a i er temperatures give lower yields of the desired esters; EXAMPLE II the esters being destroyed and more residue formed.

The mechanism of the reaction and the role of the promoter in the conversion of myrcene hydrohalides to esters using alkali metal salts of carboxylic acids, is not known. To postulate a mechanism for the reaction or the role of the promoter is difficult due to the fact that the chemistry of some of the phosphorus compounds is confusing or not known. For example, see the reactions of phosphorus trichloride with ammonia in J. W. Mellor,

Into a one liter flask equipped with an agitator, thermometer, gas inlet tube and sealed to the air by a hubbling tube containing 1 inch of heavy mineral oil, was charged 250 g. myrcene, distilled and 2.5 g. of cupric acetate. The flask was evacuated and 56 g. anhydrous hydrogen chloride was passed in over the surface at 10 C. over a 5 hour period with cooling and vigorous agitation. The batch was agitated an additional /2 hour Inorganic and Theoretical Chemistry, vol. VIII, Long- 7 at 10 C. The crude chlorides amounted to 308.5 g.

(A) To the myrcene hydrochloride was added 155 g. of anhydrous sodium acetate and 3.5 g. phosphorus trichloride. The batch was heated to 70 C. and agitated at 70-75 C. for 2-0 hours.

The salts were dissolved in 600 ml. of water. The aqueous layer was extracted with 100 ml. of hexane and the hexane layer added to the oil layer. The oil-hexane layer was washed 2x 100 ml. of water, 1x 50 ml. of NaHCO The hexane was removed by distillation under slightly reduced pressure. The residual crude acetates connected to an ammonia cylinder and sealed to the air by a bubbling tube filled with 1" of heavy mineral oil is charged 10 g. phosphorus trichloride and 100 ml. of benzene. The batch is cooled at 25 C. and 8.0 g. of ammonia is added over a period of 1 hour at 25-30 C. and the batch is agitated an additionl 1 hour at 25 to 30 C. The solid is filtered, washed with 50 ml. benzene and dried under vacuum at room tempreature. The solid amounts to approximately 16 g. The solid analyzed 13.0% phosphorus, 48.2% chlorine, 27.9% nitrogen, 6.7% hyamounted to 300 g. (7.71% C1). The crude analyzed by 10 drogen, which corresponds to the phosphorus trichloride- V.P.C. as follows: ammonia addition compound, PCI -SNH (calc.: 13.9% .P rce t phosphorus, 47.8% chlorine, 31.5% nitrogen, 6.8% hy- Hydrocarbons and chlorides 60.4 d g Linalyl acetate 33.9 The phosphorus trichloride-ammonia addition com- N r l, geranyl t t 5,7 pound was also prepared in good yield following the bove procedure and using diethyl ether or diisopropyl The crude acetates were saponified as follows. Into a a one liter flask, equipped with an agitator, thermometer ether as the solvent m place of benzene and a condenser was charged 350 g. methanol, 140 g. of 50% aqueous sodium hydroxide solution. The batch was 20 EXAMPLE IV agitated and heated to reflux and the crude acetates were Into a 1 liter fl k equipped i an agitator thermolhadded Over a 10 minute p The batch figitated eter, gas inlet tube and sealed to the air by a bubbling and refluxed for 8 hours. The methanol was distilled off tube containing 1 inch f heavy mineral i was charged at atmospherlc Pressure to a P temperature of 250 of myrcene, distilled (80%) and 2.5 g. of cupric The recovered methanol was diluted with twice its weight aceta'tg The fl k was evacuated d 56 f anhydrous of water and the oil added to the batch. The crude was hydrogen hl i was passed in Over h urf at Separated and Washed 2X 100 Of Water and 2X 50 10 C. over a 4 /2 hour period. The batch was agitated ml. of saturated salt water. The crude alcohols amounted an additional 1 at 10 h crude chlorides to 255 g. The crude alcohols analyzed by V.C.P. as folamounted to 5 lows: 30 To the myrcene hydrochloride were added 159.1 g. anlPelcent hydrous sodium acetate and 10 g. of the phosphorus tri- Hydfocarbons chloride-ammonia addition compound prepared in Ex- LlnalOOl ample III. The batch was heated to 90 C. and agitated Terpen e e s at 90-95 C. for 6 hours. Samples were taken at inter- Terpineol and isomers 1.1 vals during the agitation period, washed, dried and analy- Nerol, geraniol 3-7 zed by V.P.C.

Total Percent Percent Percent Total percent Agitation Hydro- Percent Terpinyl Neryl, LinalyLNeryl, Time Carbon and Linal Acetate Geranyl Geranyl Sample (Hrs.) Chlorides Acetate and Isomers Aoetates Acetates 1 1 22. 6 59. 2 2. 7 15. 5 74. 7 2 2 21. s 60. 4 2. 1 15. 7 76. 1 3 4 21. 4 59. 7 3.6 15. a 75. 0 4 e 21. 9 60. 2 2. 1 15. s 76. 0

(B) M rcene hydrochlorides (308.5 g), P p as The salts were dissolved in 600 ml. of water. The described a 5 g. anhydr sodium acetate, 8- aqueous layer was extracted with 100 ml. of hexane and Cupruos chloride and Phosphorus trichlol'ide were the hexane layer added to the oil layer. The oi1-hexane agitated and heated at for 17 The layer was washed 2X 100 ml. of water, 1X 50 ml. of t n was Worked P for estersfis descnbed abqve and 10% NaHCO The hexane was removed by distillation g 307 crude esters containing 4.3% ChlOTlIle and under slightly reduced pressure. The residual crude ace- Whlch analyzed by as follows: tates amounted to 311 g. (2.4% Cl). The crude analyzed Percent by V.P.C. as follows: Hydrocarbons and chlondes 36.5 Linalyl acetate 52,8 1 e Percent Terpinyl acetates 1 2 Hydrocarbons and chlorides 22.6 Neryl, geranyl acetate 9-5 Linalyl acetate 60.2 s onifi ation of th crude esters as described above p y acetates and isomers gave 255 g. crude alcohols which analyzed by V-P-C- a Neryl, geranyl acetates 15.2 follows:

Percent The crude acetates were saponified as follows: Into a Hydrocarbons and terpene ethers 552 one liter flask, equipped with an agitator, thermometer, Linalool and a condenser was charged 350 g. methanol, 140 g. of Terpineol and isomers 2.5 50% aqueous sodium hydroxide solution. The batch was Nerol, geraniol agitated and heated to reflux and the crude acetates were Purification of the crude alcohols prepared using PCl as catalyst established that the highest weight yields that could be obtained were about 30% linalool and 10% nerol, geraniol, based on 100% myrcene.

EXAMPLE IH Into a small flask equipped with an agitator, thermometer, a gas inlet tube for above surface feed wh1ch1s 7 amounted to 255 g. (0.44% C1). The crude alcohols analyzed by V.P.C. as follows:

8 rated and washed 2X 100 ml. of water and 2X 50 ml. saturated salt water. The crude alcohols amounted to 259 Percent g. (0.6% C1). The crude alcohols analyzed by V.P.C. as Hydrocarbon 22.4 follows: Linalool 59.7 Percent Terpineols and isomers 2.8 5 Hydrocarbons and chlorides 33.5 Nerol, geraniol 15.1 Linalool 48.4 The crude alcohols were vacuum distilled at 5 mm. Terpllneols i lsomers using a 37 cm. column packed with glass helices. The frac- Nero geramol tions were analyzed by V.P.C. and the yield of alcohols 10 The crude alcohols were vacuum distilled at 5 mm. calculated on the basis of 100% myrcene charged. using a 37 cm. column packed with glass helices. The frac- The weight yields were 64.7% linalool and 15.2% nerol, tions were analyzed by V.P.C. and the yield of alcohols geraniol. calculated on the basis of 100% myrcene charged.

The total weight yield was 79.9% linalool, nerol, gera- The weight yields were 54.2% linalool and 14.0% niol based on 100% myrcene charged. nerol, geraniol.

EXAMPLE V The total weight yield was 68.2% linalool. nerol, gera- Into a 1 liter flask equipped with an agitator thermomniol based on 100% myrcene charged. eter, gas inlet tube and sealed to the air by a bubbling EXAMPLE VI tube containing 1 inch of heavy mineral oil, was charged 2() Into a 1 liter flask equipped with an agitator, thermom- 250 g. of myrcene, distilled (80%) and 2.5 g. of cupric eter, gas inlet tube and sealed to the air by a bubbling acetate. The flask was evacuated and 56 g. of anhydrous tube containing 1 inch of heavy mineral oil, was charged hydrogen chloride was passed in over the surface of 10 C. 250 g. of myrcene, distilled 80%) and 2.5 g. of cupric over a 4 hour period. The batch was agitated an addiacetate. The flask was evacuated and 56 g. of anhydrous tional /2 hour at 10 C. The crude chlorides amounted to hydrogen chloride was passed in over the surface at 10 C. 308.5 g. over a 4 /2 hour period. The batch was agitated an addi- To the myrcene hydrochloride were added 152.5 g. tional /2 hour at 10 C. The crude chlorides amounted anhydrous sodium acetate and 5.0 g. of the phosphorus to 308.5 g. trichloride-ammoniaaddition compound prepared in Ex- To the myrcene hydrochloride was added 159.1 g. anample III. The batch was heated to 90 C. and agitated hydrous sodium acetate and the batch agitated at 10 C. at 9095 C. for 6% hours. Samples were taken at interfor 15 minutes. 6.18 g. Phosphorus trichloride was added vals during the agitation period, washed, dried and anaand 3.82 g. of ammonia gas was passed in over the surface lyzed by V.P.C. at 10 C. over a 22 minute period with vigorous agitation.

Total Percent Percent Percent Total percent Agitation Hydro- Percent Terpinyl Neryl Linalyl,Neryl, Time carbon and Linalyl acetate Geranyl Geranyl Sample (Hrs) Chlorides Acetate and Isomers Acetates Acetates The salts were dissolved in 600 ml. of water. The aque- The batch was heated to 90 C. and agitated at 90-95 C.

ous layer was extracted with 100 ml. of hexane and the hexane layer added to the oil layer. The oil-hexane layer for 7 /3 hours. Samples were taken at intervals during the agitation period, washed, dried and analyzed by V.P.C.

was washed 2X 100 ml. of water, 1X ml. of 10% NaHCO The hexane was removed by distillation under slightly reduced pressure. The residual crude acetates amounted to 315 g. (3.5% Cl). The crude analyzed by V.P.C. as follows: 24.5% hydrocarbons and chlorides, 56.4% linalyl acetate, 2.6% terpinyl acetates and isomers, 16.4% neryl, geranyl acetates.

The crude acetates were saponified as follows: Into a one liter flask, equipped with an agitator, thermometer, and a condenser was charged 350 g. methanol, 140 g. of 50% aqueous sodium hydroxide solution. The batch was agitated and heated to reflux and the crude acetates were added over a 10 minute period. The batch was agitated and refluxed for 8 hours. The methanol was distilled ofl at atmospheric pressure to a pot temperature of 95 C. The recovered methanol was diluted with twice its weight of water and the oil added to the batch. The crude was sepa- V.P.C. as follows:

Percent Hydrocarbons and chlorides 20.0 Linalyl acetate 59.4 Terpinyl acetates and isomers 0.9 Neryl, geranyl acetates 19.7

The crude acetates were saponified as follows: Into a one liter flask, equipped with an agitator, thermometer, and a condenser was charged 350 g. methanol, g. of 50% aqueous sodium hydroxide solution. The batch was agitated and heated to reflux and the crude acetates were added over a 10 minute period. The batch was agitated and refluxed for 8 hours. The methanol was distilled oil at atmospheric pressure to a pot temperature of 95 C. The recovered methanol was diluted with twice its weight of water and the oil added to the batch. The crude was separated and washed 2x 100 ml. of water and 2X 50 ml. saturated salt water. The crude alcohol amounted to 250 g. (0.53% C1).

The crude alcohol analyzed by V.P.C. as follows:

Percent Hydrocarbons and chlorides 24.4 Linalool 59.5 Terpineol and isomers 1.2 Nerol, geraniol 14.9

The crude alcohol was vacuum distilled at 5 mm. using a 37 cm. column packed with glass helices. The fractions were analyzed by V.P.C. and the yield of alcohols calculated on the basis of 100% myrcene charged.

The weight yields were 59.6% linalool and 15.9% nerol, geraniol.

The total weight yield was 75.5% linalool, nerol, geraniol based on 100% myrcene charged.

EXAMPLE VII Into a 1 liter flask equipped with an agitator, thermometer, gas inlet tube and sealed to the air by a bubbling tube containing 1 inch of heavy mineral oil, was charged 250 g. of myrcene, distilled (80%) and 2.5 g. of cupric acetate. The flask was evacuated and 56 g. of anhydrous hydrogen chloride was passed in over the surface at C. over a 4 /2 hour period. The batch was agitated an additional /2 hour at 10 C. The crude chlorides amounted to 308.5 g.

To the myrcene hydrochloride, were added 2.5 g. cuprous chloride and 159.1 g. anhydrous sodium acetate and the batch was agitated minutes at 10 C. 6.18 g. Phosphorus trichloride was added and 3.82 g. ammonia gas was passed in at 10 C. over a 10 minute period with vigorous agitation. The batch was heated to 75 C. and agitated at 75 C. for 8 hours.

Samples were taken at intervals during the agitation period, washed, dried and analyzed by V.P.C.

mm. using a 37 cm. column packed with glass helices. The fractions were analyzed by V.P.C. and the yield of esters calculated on the basis of 100% myrcene charged.

The weight yields were 70.7% linalyl acetate and 26.8% neryl, geranyl acetates.

The total weight yield was 97.5% linalyl, neryl, geranyl acetates based on the weight of 100% myrcene charged.

The foregoing illustrates the practice of this invention, which, however, is not to be limited thereby but is to be construed as broadly as permissible in view of the prior art and limited solely by the appended claims.

What is claimed is:

1. A process for preparing esters which comprises reacting at least one member of the group consisting of myrcene hydrohalide, linalyl halide, neryl halide and geranyl halide with a fatty acid salt in the presence of an addition compound of 1 mole of phosphorus trichloride and 5 moles of ammonia as a catalyst.

2. A process in accordance with claim 1, wherein said member is myrcene hydrohalide.

3. A process in accordance with claim 2, wherein the fatty acid salt is sodium acetate.

4. A process in accordance with claim 2, in which from about 1 to 1.5 mols of fatty acid salt and from about 0.001 to 0.1 mol of catalyst per mol of myrcene halide are employed and the reaction is conducted at a temperature within the range from about C. to 100 C.

5. A process in accordance with claim 4, wherein myrcene hydrochloride is said member and sodium acetate is the fatty acid salt.

6. A process in accordance with claim 5, wherein cuprous chloride is also used.

7. A process in accordance with claim 5, wherein about 300 parts of myrcene hydrochloride and about 160 parts of sodium acetate were reacted in the presence of about 5 to 10 parts of PCI .(NH at a temperature within the range from about C. to C.

8. A process in accordance with claim 7, wherein the PCl .(NH was formed in situ.

9. A process in accordance with claim 8, wherein cuprous chloride is also used.

Total Percent Percent Percent Total percent Agitation Hydro- Percent Terpinyl Neryl, LlnalyLNeryl, Time Carbon and Linalyl Acetate Geranyl Geranyl Sample (Hrs.) Ohlorides Acetate and Isomers Acetates Acetates The salts were dissolved in 600 ml. of water. The References Cited aqueous layer was extracted with ml. of hexane and 55 UNITED STATES PATENTS the hexane layer added to the oil layer. The oil-hexane layer was washed 2 100 ml. of water, 1X 50 ml. of 3,076,839 2/1963 Webb 250*489 3,293,286 12/1966 Webb 260-489 10% NaHCO The hexane was removed by distillation under slightly reduced pressure. The residual crude esters amounted to 315 g. (0.96% C1). The crude analyzed by V.P.C. as follows: 19.4% hydrocarbons and chlorides 59.3% linalyl acetate, 1.0% terpinyl acetates and isomers, 20.3 neryl, geranyl acetates.

The crude acetate mixture was vacuum distilled at 5 JAMES A. PATTEN, Primary Examiner 60 V. GARNER, Assistant Examiner U.S. Cl. X.R. 23-87; 252-435 

